Emission Treatment Systems and Methods

ABSTRACT

Exhaust treatment filters, systems, and methods are disclosed. According to one or more embodiments, a particulate filter is zone coated with an oxidation catalyst and is used in an emission treatment system or method including a NOx reducing catalyst and an optional NH 3  destruction catalyst.

CROSS REFERENCE TO RELATED APPLICATION

This application claims priority to U.S. Provisional Patent ApplicationSer. No. 60/868,289, filed on Dec. 1, 2006, U.S. Provisional PatentApplication Ser. No. 60/868,293, filed Dec. 1, 2006, and U.S.Provisional Patent Application Ser. No. 60/870,323, filed Dec. 15, 2006,the disclosures of which are hereby incorporated by reference in theirentirety.

FIELD OF THE INVENTION

Embodiments of the invention relate generally to diesel exhausttreatment filters, systems, and methods. More particularly, embodimentsof the present invention pertain to diesel exhaust treatment systems andmethods that include coated particulate filters coated with an oxidationcatalyst.

BACKGROUND

Compression ignition diesel engines have great utility and advantage asvehicle power trains because of their inherent fuel economy and hightorque at low speed. Diesel engines run at a high air to fuel (A/F)ratio under very fuel lean conditions. Because of this, they have verylow emissions of gas phase hydrocarbons and carbon monoxide. However,diesel exhaust is characterized by relatively high emissions of nitrogenoxides (NO_(x)) and particulates. Diesel engine exhaust is aheterogeneous mixture which contains not only gaseous emissions such ascarbon monoxide (“CO”), unburned hydrocarbons (“HC”) and nitrogen oxides(“NO_(x)”), but also condensed phase materials (liquids and solids)which constitute the so-called particulates or particulate matter.Emissions treatment systems for diesel engines must treat all of thecomponents of the exhaust to meet emissions standards set by variousregulatory agencies throughout the world.

The total particulate matter emissions of diesel exhaust contain threemain components. One component is the solid, dry, carbonaceous fractionor soot fraction. This dry carbonaceous fraction contributes to thevisible soot emissions commonly associated with diesel exhaust. A secondcomponent of the particulate matter is the soluble organic fraction(“SOF”). The SOF can exist in diesel exhaust either as a vapor or as anaerosol (fine droplets of liquid condensate) depending on thetemperature of the diesel exhaust. It is generally present as condensedliquids at the standard particulate collection temperature of 52° C. indiluted exhaust, as prescribed by a standard measurement test, such asthe U.S. Heavy Duty Transient Federal Test Procedure. These liquidsarise from two sources: (1) lubricating oil swept from the cylinderwalls of the engine each time the pistons go up and down; and (2)unburned or partially burned diesel fuel. The third component of theparticulate matter is the so-called sulfate fraction, which is formedfrom small quantities of sulfur components present in the diesel fuel.

Catalyst compositions and substrates on which the compositions aredisposed are typically provided in diesel engine exhaust systems toconvert certain or all of these exhaust components to innocuouscomponents. For instance, oxidation catalysts, which may be referred toas diesel oxidation catalysts (DOCs), containing platinum group metals,base metals and combinations thereof, facilitate the treatment of dieselengine exhaust by promoting the conversion of both unburned hydrocarbons(HC) and carbon monoxide (CO) gaseous pollutants, and some proportion ofthe particulate matter through oxidation of these pollutants to carbondioxide and water. Such catalysts have generally been disposed onvarious substrates (e.g., honeycomb flow through monolith substrates),which are placed in the exhaust of diesel engines to treat the exhaustbefore it vents to the atmosphere. Certain oxidation catalysts alsopromote the oxidation of NO to NO₂.

In addition to the use of oxidation catalysts, diesel particulatefilters are used to achieve high particulate matter reduction in dieselemissions treatment systems. Typical ceramic wall flow filter substratesare composed of refractory materials such as cordierite orsilicon-carbide. Wall flow substrates are particularly useful to filterparticulate matter from diesel engine exhaust gases. A commonconstruction is a multi-passage honeycomb structure having the ends ofalternate passages on the inlet and outlet sides of the honeycombstructure plugged. This construction results in a checkerboard-typepattern on either end. Passages plugged on the inlet axial end are openon the outlet axial end. This permits the exhaust gas with the entrainedparticulate matter to enter the open inlet passages, flow through theporous internal walls and exit through the channels having open outletaxial ends. The particulate matter is thereby filtered on to theinternal walls of the substrate. The gas pressure forces the exhaust gasthrough the porous structural walls into the channels closed at theupstream axial end and open at the downstream axial end. Theaccumulating particles will increase the back pressure from the filteron the engine. Thus, the accumulating particles have to be continuouslyor periodically burned out of the filter to maintain an acceptable backpressure.

Catalyst compositions deposited along the internal walls of the wallflow substrate assist in the regeneration of the filter substrates bypromoting the combustion of the accumulated particulate matter. Thecombustion of the accumulated particulate matter restores acceptableback pressures within the exhaust system. Soot combustion can be passive(e.g., with catalyst on the wall flow filter and adequately high exhausttemperatures), though for many applications active soot combustion isalso required (e.g., production of a high temperature exotherm in theexhaust up-stream of the filter). Both processes utilize an oxidant suchas O₂ or NO₂ to combust the particulate matter.

Passive regeneration processes combust the particulate matter attemperatures within the normal operating range of the diesel exhaustsystem. Preferably, the oxidant used in the regeneration process is NO₂since the soot fraction combusts at much lower temperatures than thoseneeded when O₂ serves as the oxidant. While O₂ is readily available fromthe atmosphere, NO₂ can be generated through the use of upstreamoxidation catalysts to oxidize NO in the exhaust stream. An example of apassive regeneration process is disclosed in U.S. Pat. Nos. 6,753,294and 7,097,817.

Active regeneration processes are generally needed to clear out theaccumulated particulate matter, and restore acceptable back pressureswithin the filter. The soot fraction of the particulate matter generallyrequires temperatures in excess of 500° C. to burn under oxygen rich(lean) conditions, which are higher temperatures than those typicallypresent in diesel exhaust. Active regeneration processes are normallyinitiated by altering the engine management to raise temperatures infront of the filter up to 500-630° C. Depending on driving mode, highexotherms can occur inside the filter when the cooling duringregeneration is not sufficient (low speed/low load or idle drivingmode). Such exotherms may exceed 800° C. or more within the filter. Onecommon way that has been developed to accomplish active regeneration isthe introduction of a combustible material (e.g., diesel fuel) into theexhaust and burning it across a flow-thru diesel oxidation catalyst(DOC) mounted up-stream of the filter. The exotherm from this auxiliarycombustion provides the sensible heat (e.g. about 500-700° C.) needed toburn soot from the filter in a short period of time (e.g. about 2-20min.).

An example of a system is shown in U.S. Pat. No. 6,928,806. The DOCfunctions during the active regeneration mode to light-off and burn fuelinjected into the low temperature (e.g., about 250-300° C.) exhaust(directly or via the engine) and thereby produce an exotherm to heat theexhaust entering the particulate filter to the temperatures required(about 500-650° C.) to combust accumulated soot from the filter, therebyregenerating the filter to reduce the operating pressure drop across thefilter associated with the soot accumulation.

High material costs associated with platinum group metal-containingcompositions augment the need to slow or prevent the degradation ofcatalyst coatings due to active regeneration events. Catalyst coatingsdisposed on wall flow filters often contain platinum group metalcomponents as active catalyst components to ensure acceptableconversions of the gaseous emissions (HC, CO) of the diesel exhaust toinnocuous components (e.g., CO₂, H₂O). The loadings of such componentsare generally adjusted so that the catalyst substrate meets emissionsregulations even after catalyst aging. Consequently, coating designsthat maximize the efficiency and durability of platinum group metalusage along the substrate are desirable.

Certain conventional coating designs for wall flow substrates have ahomogeneous distribution of catalyst coating along the entire axiallength of the internal walls. In such designs the platinum group metalconcentrations are typically adjusted to meet the emissions requirementsunder the most stringent conditions. Most often such conditions refer tothe catalyst's performance after the catalyst has aged. The costassociated with the required platinum group metal concentration is oftenhigher than is desired.

As can be appreciated from the above, current particulate filter systemspose a number of issues concerning precious metals material costs anddegradation of the catalyst on the particulate filter due to exposure tohigh temperatures. Accordingly, it would be desirable to providealternatives diesel engine in exhaust treatment systems and methods thatalleviate one or more of these issues.

SUMMARY

According to an embodiment of the invention, an emission treatmentsystem for treatment of an exhaust stream comprising NOx and particulatematter is provided, which comprises a particulate filter having an axiallength and elements for trapping particulate matter contained in anexhaust stream flowing through the filter and a light-off oxidationcatalyst composition extending from the inlet end towards the outlet endto a length that is less than the axial length of the walls to providean inlet zone in an amount sufficient to light-off at a temperature lessthan about 300° C. and generate an exotherm to burn soot trapped in thefilter; and a NOx reducing catalyst located upstream of the wall flowmonolith. In certain embodiments, the system may include an NH₃destruction catalyst located downstream from the NOx reducing catalyst.In one embodiment, the particulate filter may comprise a wall flowmonolith disposed within the exhaust stream and having a plurality oflongitudinally extending passages bounded by longitudinally extendingwalls, the passages comprising inlet passages having an open inlet endand a closed outlet end, and outlet passages having a closed inlet endand an open outlet end, the walls having a porosity of at least 40% withan average pore size of at least 5 microns and the wall flow monolithcomprising a light-off oxidation catalyst composition permeating thewalls and extending from the inlet end towards the outlet end to alength that is less than the axial length of the walls to provide aninlet zone.

In one or more embodiments, the NOx reducing catalyst comprises a leanNOx catalyst. In embodiments including a lean NOx catalyst, the systemmay further comprise a reductant introduction port in fluidcommunication with a hydrocarbon reductant, the reductant introductionport located upstream from the lean NO_(x) catalyst. The lean NOxcatalyst can also be incorporated into the oxidationcatalyst/particulate filter by zoning or layering. In other embodiments,the NOx reducing catalyst comprises a lean NO_(x) trap.

In one or more embodiments, the NOx reducing catalyst comprises an SCRcatalyst. In one or more embodiments including an SCR catalyst, thesystem may include an optional introduction port located upstream fromthe SCR catalyst, the introduction port is in fluid communication withan ammonia or ammonia precursor. The system may further include aninjector in fluid communication with the introduction port, the injectorconfigured to periodically meter the ammonia or an ammonia precursorinto the exhaust stream.

In one or more embodiments, the system may further include an NH₃destruction catalyst located downstream from the SCR catalyst. Incertain embodiments, the NH₃ destruction catalyst may be coated on theparticulate filter. The system may also include an exotherm-producingagent introduction port located upstream of the wall flow monolith, theexotherm-producing agent introduction port in fluid communication withan exotherm-producing agent capable of generating a temperaturesufficient to periodically burn particulate accumulated in the wall-flowmonolith. The exotherm-producing agent may comprise a fuel such asdiesel fuel.

Another embodiment of the invention pertains to a method of treating anexhaust stream from a diesel engine. In one embodiment, the methodcomprises disposing within the exhaust stream containing particulatematter a wall flow monolith and having a plurality of longitudinallyextending passages bounded by longitudinally extending walls, thepassages comprising inlet passages having an open inlet end and a closedoutlet end, and outlet passages having a closed inlet end and an openoutlet end, the walls having a porosity of at least 40% with an averagepore size of at least 5 microns and the wall flow monolith comprising alight-off oxidation catalyst composition permeating the walls andextending from the inlet end towards the outlet end to a length that isless than the axial length of the walls to provide an inlet zone. Themethod may further comprise disposing a NOx reducing catalyst upstreamof the wall flow monolith and periodically introducing anexotherm-producing agent upstream of the wall flow monolith to generatean exotherm in the wall flow monolith sufficient to combust particulatematter trapped within the wall flow monolith.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A is a schematic illustration of an emission treatment system inaccordance with an embodiment of the invention;

FIG. 1B is a schematic illustration of an emission treatment system inaccordance with another embodiment of the invention;

FIG. 1C is a schematic illustration of an emission treatment system inaccordance with another embodiment of the invention;

FIG. 2 is a perspective view of a wall flow filter substrate;

FIG. 3 is a section view of a wall flow filter substrate;

FIG. 4 shows an embodiment of a system including urea reservoir andinjector;

FIG. 5 is a graph showing particulate filter out exhaust gas temperatureas a function of test run time with supplemental diesel fuel injectedinto the exhaust up stream of the particulate filter;

FIG. 6 is a graph showing particulate filter out exhaust gas temperatureas a function of supplemental diesel fuel injected into the exhaust upstream of the particulate filter;

FIG. 7 is a diagram showing the location of thermocouples installedwithin the particulate filter substrate for measurement of internaltemperatures;

FIG. 8 is a graph showing internal particulate filter temperatures as afunction of location in the particulate filter, plus inlet and outletexhaust gas temperatures, during a fuel light-off test;

FIG. 9 is a graph showing exhaust temperatures and Delta P across aparticulate filter during an active regeneration test with soot loadedin the particulate filter; and

FIG. 10 is a schematic view of a system used in Example 5.

DETAILED DESCRIPTION Definitions

The following terms shall have the meanings set for below according toembodiments of the invention:

“Activated alumina” has its usual meaning of a high BET surface areaalumina, comprising one or more of gamma-, theta- and delta aluminas.

“BET surface area” has its usual meaning of referring to the Brunauer,Emmett, Teller method for determining surface area by N₂ absorption.Unless otherwise specifically stated, all references herein to thesurface area of the catalyst support components or other catalystcomponents means the BET surface area.

“Bulk form,” when used to describe the physical form of a material(e.g., ceria), means the material is present as discrete particles thatcan be as small as 1 to 15 microns in diameter or smaller, as opposed tohaving been dispersed in solution onto another material such as gammaalumina. By way of example, in some embodiments of the invention,particles of ceria are admixed with particles of gamma alumina so thatceria is present in bulk form, as opposed to, for example, impregnatingalumina particles with aqueous solutions of ceria precursors which uponcalcination are converted to ceria disposed on the alumina particles.

“Cerium component” means one or more oxides of cerium (e.g., CeO₂).

“Downstream” and “Upstream,” when used to describe an article, catalystsubstrate or zone, refer to the relative positions in the exhaust systemas sensed in the direction of the flow of the exhaust gas stream.

“High surface area support” means support materials with a BET surfacearea that is approximately greater than 10 m²/g, preferably greater than150 m²/g.

“Platinum group metal component” or “PGM” refers to the platinum groupmetals or oxides thereof. Preferred platinum group metal components areplatinum, palladium, rhodium iridium components, and combinationsthereof.

“Diesel oxidation catalyst” or “DOC” refers to a catalyst promotingoxidation processes in diesel exhaust, to reduce emissions of theorganic fraction of diesel particulates, gas-phase hydrocarbons, and/orcarbon monoxide.

“Active regeneration” refers to the introduction of a combustiblematerial (e.g., diesel fuel) into the exhaust and burning it across anoxidation catalyst to generate an exotherm from that provides heat (e.g.about 500-700° C.) needed to burn particulate matter such as soot fromthe filter.

An ammonia destruction catalyst or AMOX refers to a catalyst thatpromotes the oxidation of NH₃ to ideally nitrogen but in general to amixture of nitrogen NOx and N₂O.

“Particulate filter” is a filter designed to remove particulate matterfrom an exhaust gas stream such as soot, and particulate filtersinclude, but are not limited to honeycomb wall flow filters, partialfiltration filter, a wire mesh filter, wound fiber filters, sinteredmetal filters; and foam filters.

Before describing several exemplary embodiments of the invention, it isto be understood that the invention is not limited to the details ofconstruction or process steps set forth in the following description.The invention is capable of other embodiments and of being practiced orbeing carried out in various ways.

According to one or more embodiments of the invention, a separate,upstream light-off oxidation catalyst is eliminated from a diesel engineemission treatment system and incorporated directly onto a particulatefilter itself by placing light-off oxidation catalyst components at theinlet end of the filter channels extending an adequate length from theinlet end towards the outlet end of the filter. In this way, duringactive regeneration, the introduced combustible fuel is lit-off andburnt on the inlet end of the filter, thus producing the necessaryexotherm at a temperature of about 500-700° C. within the filter tocombust accumulated soot in the filter. In one or more embodiments, itmay be desirable to provide an auxiliary oxidation catalyst to oxidize aportion of the NOx to NO₂.

According to embodiments of the invention, active regeneration can beaccomplished by or on the filter alone, and the need for a separatelight-off oxidation catalyst in the system is eliminated. Eliminating acomponent from the system provides a benefit of eliminating a substrateand associated canning of the system. In turn, this elimination of aseparate component reduces overall system volume, and potentiallyreduces the amount of expensive precious group metal (PGM) loadingrequired for the system. Furthermore, providing an integrated light offoxidation catalyst on the particulate filter reduces the overall systemback-pressure on the engine, which is associated with fuel consumption.In addition, in systems that include a NO_(x) reducing catalyst, forexample an SCR catalyst or lean NOx catalyst downstream from theintegrated light-off oxidation catalyst/particulate filter provides agreater amount heat for these downstream devices compared to systems inwhich the light-off oxidation catalyst and particulate soot filter areprovided as separate components. The integrated light-off oxidationcatalyst/particulate filter can be moved closer to the engine. Reducingthe size of the system by integrating the oxidation catalyst and sootfilter reduces the heat loss from the particulate filtering sub-system,thereby allowing any downstream component to operate at highertemperature. Higher temperatures generally result in higher catalyticactivity, and therefore, integrating the oxidation catalyst in theparticulate filter will likely result in better performance of the NOxremoval components downstream of the particulate filtering sub-system.

Furthermore, by disposing a NOx reducing catalyst upstream of theoxidation catalyst/particulate filter, hydrocarbons can be supplied tothe NOx reducing catalyst, eliminating the need to supply a separatereductant source. In addition, a single introduction port or injectorcan be used to supply an auxiliary reductant, for example, urea, and thefuel to perform the burning of the soot in the particulate filter. Inaddition, an ammonia destruction catalyst can be integrated onto theoutlet end of the substrate having the SCR catalyst, which wouldeliminate the need for a separate ammonia destruction catalyst. Afurther benefit of placing the nitrogen reducing catalyst upstream ofthe particulate filter is that the nitrogen reducing catalyst is notexposed to the extreme temperatures associated with the activeregeneration of the particulate filter. Furthermore, when an SCR is usedas the NOx reducing catalyst, this enables a broader range of materialsto be used for the SCR catalyst composition. For example, vanadiummaterials can be used in place of or together with zeolites, to reducethe cost of the SCR catalyst.

When the NOx reducing catalyst uses NH₃ or an NH₃ precursor as thereducing agent, a separate injector can be provided upstream of the SCRcatalyst. With the fuel addition point (for filter regeneration)provided downstream of the SCR catalyst, the nitrogen reducing catalystis not exposed to the extreme temperatures associated with the activeregeneration of the particulate filter. The absence of high temperatureexposure caused by forced filter regenerations allows a smaller SCRcatalyst volume with corresponding cost saving and packaging advantages.Further, the absence of the high temperature exposure enables a broaderrange of materials to be used for the SCR catalyst composition. Forexample, vanadium materials can be used in place of or together withzeolites, to reduce the cost of the SCR catalyst and improve itseffectiveness. In addition, an ammonia destruction catalyst can beintegrated onto the outlet end of the substrate having the SCR catalyst,which would eliminate the need for a separate ammonia destructioncatalyst. In a further system optimization, the NH₃ destruction catalystcan be integrated into the soot filter either as zone or a uniformcoating. By doing so, the overall system volume is reduced with acorresponding cost and packaging advantages.

Integration of the light-off/oxidation catalyst function and particulateremoval functions into a single catalyst article is accomplished using awall flow substrate coated with a light-off oxidation catalystcomposition. The light-off/oxidation catalyst composition contains asufficient loading of precious group metal composition to achievelight-off at a temperature less than about 300° C. (e.g, from about 220°C. to 300° C.) to generate an exotherm to burn soot collected in thefilter. Temperatures generated by the exotherm typically are betweenabout 500° C. and 700° C. Although there may be a number of ways toincorporate the light-off/burning function onto the particulate filteritself, one method would be to apply this function to the particulatefilter as a zone of catalyst on the up-stream, inlet end of theparticulate filter substrate (e.g. honeycomb, wall-flow filtersubstrate). This inlet catalytic zone which will be exposed torelatively low exhaust temperatures 220-300° C.) and will have to have ahigh enough catalytic activity to accomplish the light-off, plusreasonably complete combustion of the injected fuel to produce the hightemperatures, for example, about 500-700° C. required for filterregeneration. Although there are a variety of catalyst compositions thatcan accomplish this, an exemplary composition would be comprised ofprecious group metals (PGM's) dispersed on a suitable support and at aloading level suitable to light-off and burn the injected fuel, and isdescribed in more detail below. The inlet zone will typically extend atleast 10% of the axial length of the filter, and in various embodiments,the inlet zone extends at least about 20%, 25%, 30%, 35%, 40%, 45%, 50%or up to about 75% of the axial length of the filter. The inlet zone maybe directly on the walls of the filter, or the inlet zone may be formedover a catalytic coating that extends the entire axial length of thefilter. The underlying catalytic coating may be a base metal oxide suchas an oxide of copper, cobalt, chromium, cerium, etc. or a preciousgroup metal composition. In embodiments in which the underlying coatingis a precious group metal composition, the loading is typically lessthan or equal to 10 g/ft³. Thus, the particulate filter may have acatalytic coating of platinum or other suitable precious group metal ata loading of 10 g/ft³ covering the entire axial length of the walls ofthe filter and a second coating extending from the inlet end for only aportion of the axial length of the filter at a higher loading sufficientto light-off and produce the exotherm to burn off soot collected in thefilter.

An embodiment of the inventive emission treatment system is shown inFIG. 1A. As can be seen in FIG. 1A, the exhaust containing gaseouspollutants (including unburned hydrocarbons, carbon monoxide and NOx)and particulate matter is conveyed from the engine 15 to a NOx reducingcatalyst 11.

Upstream of the NOx reducing catalyst 11, a reductant, for example,ammonia, is injected as a spray via a nozzle (not shown) into theexhaust stream. Aqueous urea shown on one line 18 can serve as theammonia precursor which can be mixed with air on another line 19 in anoptional mixing station 16. An introduction port or valve 14 can be usedto meter precise amounts of aqueous urea which are converted in theexhaust stream to ammonia. The exhaust stream with the added ammonia isconveyed to a NOx-reducing catalyst 11, for example, an SCR catalyst,which may be coated on an appropriate substrate such as a honeycombfilter. On passing through the reducing catalyst 11, the NOx componentof the exhaust gas stream is converted through the selective catalyticreduction of NOx with ammonia to nitrogen. As noted above, if the NOxreducing catalyst is a lean NOx catalyst, a separate reductant does notnecessarily need to be injected into the system, and the reductant canbe a hydrocarbon reductant supplied from the engine.

Depending on the desired level of NOx removal, one or more NOx reducingcatalysts can be disposed downstream of the NOx reducing catalyst 11.For example, the additional SCR catalyst may be disposed on amonolithic, honeycomb flow through substrate, a ceramic foam substrateor metallic substrate downstream of the NOx reducing catalyst 11.

Downstream from the NOx reducing catalyst 11 is a particulate filter 12,for example, a wall flow monolith comprising wall elements having alight-off oxidation catalyst composition permeating at least an inletzone of the walls, as will described further below. In the light-offoxidation catalyst permeating the walls of the particulate filter 12,unburned gaseous and non-volatile hydrocarbons (i.e., the SOF) andcarbon monoxide are largely combusted to form carbon dioxide and water.Removal of substantial proportions of the SOF using the oxidationcatalyst, in particular, helps prevent deposition of excessiveparticulate matter on the particulate filter 12, which could becomeclogged by excessive particulate matter. In addition, a substantialproportion of the NO of the NOx component is oxidized to NO₂ in theoxidation catalyst portion of the particulate filter 12. The particulatematter including the soot fraction and the VOF are also largely removed(greater than 80%) by the particulate filter. The particulate matterdeposited on the particulate filter is combusted through activeregeneration of the filter, which process is aided by the presence ofthe integrated light-off oxidation catalyst composition. Activeregeneration is initiated according to a predetermined event, forexample, after a predetermined mileage or time period, or upon sensing apredetermined back pressure in the particulate filter 12. Activeregeneration occurs when a hydrocarbon, for example, diesel fuel isinjected into a hydrocarbon introduction port 9 located upstream fromthe filter 12 and in communication with a hydrocarbon source (notshown). Of course, it will be appreciated that diesel fuel is aconvenient hydrocarbon source due to the fact that it is on board of thevehicle. A sufficient amount of hydrocarbon is introduced intointroduction port 9 to generate an exotherm to combust the soot trappedin filter 12. As those skilled in the art will appreciate, the exothermgenerated will depend on the inlet exhaust temperature into theparticulate filter, the amount of fuel injected and the precious metalloading of the particulate filter. Different precious metals willrequire different loading to generate the exotherm to burn off soottrapped in the filter.

An optional configuration is shown in FIG. 1B, where the emissiontreatment system is provided with an NH₃-destruction catalyst, such as aslip oxidation catalyst 13 downstream of the NOx reducing catalyst 11and particulate filter 12. The slip oxidation catalyst can be coated,for example, with a composition containing base metals and less than 0.5wt % of platinum. This provision can be used to oxidize any excess NH₃before it is vented to the atmosphere. According to one or moreembodiments, the NH₃-destruction catalyst may be disposed on theparticulate filter 12. Similar to the embodiment described above, ahydrocarbon introduction port 9 is located upstream of the filter tointroduce a suitable hydrocarbon such as diesel fuel to generate anexotherm to burn soot trapped in the filter 12.

In an important alternative embodiment shown in FIG. 1C, a system isshown in which a reductant, for example, ammonia, is injected as a sprayvia a nozzle (not shown) into the exhaust stream downstream from theengine 15. Similar to the embodiment shown in FIG. 1A, aqueous ureashown on one line 18 can serve as the ammonia precursor which can bemixed with air on another line 19 in an optional mixing station 16. Anintroduction port or valve 14 can be used to meter precise amounts ofaqueous urea which are converted in the exhaust stream to ammoniadownstream from the engine 15. A NOx-reducing catalyst, for example, anSCR catalyst contained on an appropriate substrate, is disposeddownstream from the reductant introduction port or valve 14. A light-offdiesel oxidation catalyst 17 is provided downstream from the NOxreducing catalyst, and a particulate filter 20 is provided downstreamfrom the diesel oxidation catalyst 17. According to this embodiment, thediesel oxidation catalyst 20 may be a separate component provided on anappropriate substrate such as a honeycomb filter. The particulate filtermay be a bare particulate filter or a catalyzed particulate filter, forexample, a catalyzed soot filter (CSF) containing precious metal alongthe entire axial length of the filter. Alternatively, the particulatefilter can be a zoned particulate filter, for example, a wall flowfilter including a zone on the inlet end containing a light off/dieseloxidation catalyst. Like in the embodiments described in FIGS. 1A and1B, a hydrocarbon introduction port 9 is located upstream of the filterto introduce a suitable hydrocarbon such as diesel fuel to generate anexotherm to burn soot trapped in the filter 12. An optional ammoniadestruction catalyst 13 may be provided downstream from the particulatefilter 20.

Wall Flow Substrates

The particulate filter may be embodied in many forms. For example, theparticulate filters may be in the form of a honeycomb wall flow filter,a partial filtration filter, a wire mesh filter, a wound fiber filter, asintered metal filters and a foam filter. In specific embodiments, theparticulate filter is a wall flow filter. Wall flow substrates usefulfor supporting the oxidation catalyst compositions have a plurality offine, substantially parallel gas flow passages extending along thelongitudinal axis of the substrate. Typically, each passage is blockedat one end of the substrate body, with alternate passages blocked atopposite end-faces. Such monolithic carriers may contain up to about 700or more flow passages (or “cells”) per square inch of cross section,although far fewer may be used. For example, the carrier may have fromabout 7 to 600, more usually from about 100 to 400, cells per squareinch (“cpsi”). The cells can have cross sections that are rectangular,square, circular, oval, triangular, hexagonal, or are of other polygonalshapes. Wall flow substrates typically have a wall thickness between0.002 and 0.1 inches. Examples of suitable wall flow substrates have awall thickness of between 0.002 and 0.015 inches.

FIGS. 2 and 3 illustrate a wall flow filter substrate 30 which has aplurality of passages 52. The passages are bounded or enclosed by theinternal walls 53 of the filter substrate. The substrate has an inletend 54 and an outlet end 56. Alternate passages are plugged at the inletend with inlet plugs 58, and at the outlet end with outlet plugs 60 toform opposing checkerboard patterns at the inlet 54 and outlet 56. A gasstream 62 enters through the unplugged channel inlet 64, is stopped byoutlet plug 60 and diffuses through channel walls 53 (which are porous)to the outlet side 66. The gas cannot pass back to the inlet side ofwalls because of inlet plugs 58.

Suitable wall flow filter substrates are composed of ceramic-likematerials such as cordierite, {acute over (α)}-alumina, silicon carbide,silicon nitride, zirconia, mullite, spodumene, alumina-silica-magnesia,aluminum titanate or zirconium silicate, or of porous, refractory metal.Wall flow substrates may also be formed of ceramic fiber compositematerials. Examples of suitable wall flow substrates are formed fromcordierite and silicon carbide. Such materials are able to withstand theenvironment, particularly high temperatures, encountered in treating theexhaust streams.

Suitable wall flow substrates for use in the inventive system includethin porous walled honeycombs (monolith)s through which the fluid streampasses without causing too great an increase in back pressure orpressure across the article. According to embodiments of the invention,ceramic wall flow substrates used in the system are formed of a materialhaving a porosity of at least 40% (e.g., from 50 to 75%) having a meanpore size of at least 5 microns (e.g., from 5 to 30 microns). In certainembodiments, the substrates have a porosity of at least 55% and have amean pore size of at least 10 microns. When substrates with theseporosities and these mean pore sizes are coated with the techniquesdescribed below, adequate levels of SCR catalyst compositions can beloaded onto the substrates to achieve excellent NOx conversionefficiency. These substrates are still able retain adequate exhaust flowcharacteristics, i.e., acceptable back pressures, despite the light-offoxidation catalyst loading. U.S. Pat. No. 4,329,162 is hereinincorporated by reference with respect to the disclosure of suitablewall flow substrates. Wall flow substrates can also be metallic, i.e.have no porosity, and the pore size is typically lower than of a wallflow filter.

The porous wall flow filter used according to embodiments of theinvention is catalyzed in that the wall of said element has thereon orcontained therein one or more catalytic materials. Catalytic materialsmay be present on the inlet side of the element wall alone, the outletside alone, both the inlet and outlet sides, or the wall itself mayconsist all, or in part, of the catalytic material. To coat the wallflow substrates with the light-off oxidation catalyst composition, thesubstrates are immersed vertically in a portion of the catalyst slurrysuch that the top of the substrate is located just above the surface ofthe slurry. In this manner, slurry contacts the inlet face of eachhoneycomb wall, but is prevented from contacting the outlet face of eachwall. This results in a portion of the walls on the inlet end of thesubstrate being coated, forming an inlet zone. The substrate is removedfrom the slurry, and excess slurry is removed from the wall flowsubstrate first by allowing it to drain from the channels, then byblowing with compressed air (against the direction of slurrypenetration), and then by pulling a vacuum from the direction of slurrypenetration. By using this technique, the catalyst slurry permeates thewalls of the substrate, yet the pores are not occluded to the extentthat undue back pressure will build up in the finished substrate. Asused herein, the term “permeate” when used to describe the dispersion ofthe catalyst slurry on the substrate, means that the catalystcomposition is dispersed throughout the wall of the substrate, and notjust on an outer surface of the wall as a coating layer. The coating canbe applied by any suitable technique, such as by immersing the substrateinto the coating a using a vacuum to draw the coating up into thechannels of the substrate, as described in U.S. Pat. Nos. 6,478,874;5,866,210 and 5,963,832, the entire content of each patent incorporatedherein by reference.

After coating with catalyst, the substrates are dried typically at leastabout 100° C. and calcined at a higher temperature (e.g., 300 to 450°C.). After calcining, the catalyst loading can determined be throughcalculation of the coated and uncoated weights of the substrate. As willbe apparent to those of skill in the art, the catalyst, loading can bemodified by altering the solids content of the coating slurry.Alternatively, repeated immersions of the substrate in the coatingslurry can be conducted, followed by removal of the excess slurry asdescribed above.

Oxidation Catalyst Compositions

The oxidation catalyst formed on the particulate filter can be formedfrom any composition that provides effective combustion of unburnedgaseous and non-volatile hydrocarbons (i.e., the SOF) and carbonmonoxide. In addition, the oxidation catalyst should be effective toconvert a substantial proportion of the NO of the NOx component to NO₂.As used herein, the term “substantial conversion of NO of the NOxcomponent to NO₂” means at least 20%, and preferably between 30 and 60%.Catalyst compositions having these properties are known in the art, andinclude platinum group metal- and base metal-based compositions. Anexample of oxidation catalyst composition that may be used in theemission treatment system contains a platinum group component (e.g.,platinum, palladium or rhodium components) dispersed on a high surfacearea, refractory oxide support (e.g., γ-alumina. A suitable platinumgroup metal component is platinum.

Platinum group metal-based compositions suitable for use in forming theoxidation catalyst are also described in U.S. Pat. No. 5,100,632 (the'632 patent) hereby incorporated by reference. The '632 patent describescompositions that have a mixture of platinum, palladium, rhodium, andruthenium and an alkaline earth metal oxide such as magnesium oxide,calcium oxide, strontium oxide, or barium oxide with an atomic ratiobetween the platinum group metal and the alkaline earth metal of about1:250 to about 1:1, and preferably about 1:60 to about 1:6.

Catalyst compositions suitable for the oxidation catalyst may also beformed using base metals as catalytic agents. For example, U.S. Pat. No.5,491,120 (the disclosure of which is hereby incorporated by reference)discloses oxidation catalyst compositions that include a catalyticmaterial having a BET surface area of at least about 10 m²/g and consistessentially of a bulk second metal oxide which may be one or more oftitania, zirconia, ceria-zirconia, silica, alumina-silica, and {acuteover (α)}-alumina.

Also useful are the catalyst compositions disclosed in U.S. Pat. No.5,462,907 (the '907 patent, the disclosure of which is herebyincorporated by reference). The '907 patent teaches compositions thatinclude a catalytic material containing ceria and alumina each having asurface area of at least about 10 m²/g, for example, ceria and activatedalumina in a weight ratio of from about 1.5:1 to 1:1.5. Alternatively,palladium in any desired amount may be included in the catalyticmaterial. Additional useful compositions are disclosed in U.S. Pat. No.7,078,074, the entire content of which is incorporated herein byreference.

The PGM loading on the inlet zone can be varied to between about 20g/ft³ and 200 g/ft³, more specifically between about 30 g/ft³ and 150g/ft³, and in a specific embodiment between about 40 g/ft³ and 100g/ft³. These amounts can be incrementally varied in amounts of 5 g/ft³between these ranges. In specific embodiments, the PGM is can be chosenfrom Pt and/or Pd, both of which are good oxidation catalysts forhydrocarbons. The current price of platinum is much higher than forpalladium, thus the latter offers the advantage of reduced cost;however, this may change in the future depending on PGM demand. Platinumis very active for hydrocarbon oxidation reactions and is ratherresistant to poisoning. Palladium can be less active and is susceptibleto poisoning, e.g. by sulfur. However, under lean exhaust conditions andtemperatures that might exceed 800° C., platinum can experience thermalsintering and thereby reduction in oxidation activity. Addition ofpalladium and its interaction with the platinum results in a substantialreduction in the high temperature sintering of the platinum and therebymaintenance of its oxidation activity. If the temperatures of exposureare kept low, Pt-only may be a good option to obtain the highestpossible oxidation activity. However, in configurations in which hightemperatures (e.g. 800° C.) are anticipated, especially internal to thefilter, inclusion of some Pd is desired. Pt:Pd ratios to obtainacceptable Pt stability with the highest oxidation activity are betweenabout 10:1 and 4:1; however, ratios as low as 2:1 and 1:1 are alsowithin the scope of the invention. Higher Pd contents (e.g., 1:2) arealso within the scope of the present invention. In certain embodiments,Pd with no platinum may be used.

The PGM is dispersed on a suitable support material such as a refractoryoxide with high surface area and good thermal stability such as a highsurface area aluminum oxide. High surface area aluminas are suitablesupports for PGM and SBa-150 (Sasol North America) with surface area of138-158 m²/g and pore volume of 0.44-0.55 cm³/g (N₂) is an example of asuitable alumina support. Also aluminas stabilized with a second oxideare suitable supports. Lanthana stabilization of alumina provides asuitable support for PGM. For example GA-200L (4 wt. % La₂O₃) stabilizedalumina (Engelhard, Port Allen, La.) with surface area of 190-250 m²/gand pore volume of 0.5 cm³/g (N₂) is a suitable stabilized alumina. Alsomixtures of aluminas are suitable supports, for example 50:50 wt.SBa-150 plus GA-200L. Other aluminas that are doped or treated withoxides such as SiO₂, ZrO₂, TiO₂, etc.) to provide stabilization orimproved surface chemistries can also be utilized. Other suitablesupport materials, include, but are not limited to ZrO₂ and TiO₂ can beused. In addition to the PGM support oxides discussed above it mightprove useful to include other catalytically functional oxides toincorporate into the catalytic zone. Examples of these include CeO₂,Pr₆O₁₁, V₂O₅, and MnO₂ and combinations thereof and solid solution oxidemixtures, etc. These oxides can contribute to burning of hydrocarbons,especially heavy fuel derived hydrocarbons, and deposited coke/sootderived from disproportination (i.e., dehydrogenation or oxidativedehydrogenation) of the injected fuel and in this way give additionalcombustion activity to the catalytic zone, plus prevent deactivation ofthe PGM by the deposition hydrocarbon derived coke.

The loading of the oxidation catalyst in the zone on the filtersubstrate is typically is limited to control the contribution of thephysical volume of the catalyst coating filling the pore volume of thefilter substrate and thereby adversely affecting the flow resistancethrough the filter wall and thus the back-pressure. On the other hand,with high loadings of PGM on the support oxide we have to providesufficient surface area for good PGM dispersion. As an example, a PGMloading on the inlet zone of about 60 g/ft³, a dry gain (DG) of 0.5g/in³ in the zone is acceptable. The DG can be adjusted taking intoconsideration the optimum PGM loading, alumina to other (denser) oxideweight ratio, and other factors.

The ratio of the zone length/volume to total filter length/volume canvary between about 0.20 to 0.9, for example, this value can be 0.25, 0.5or 0.75. Thus for example, an 11.25″ diameter×14.0″ long filtersubstrate a zone length/depth of ca. 3.0″ could be used or a ratio of0.21 of total length/volume of the filter. However, determination of themost effective zone length/volume ratio will be part of catalyzed filteroptimization for a particular exhaust system design.

The inlet catalytic zone (length/volume ratio can vary) for light-offand combustion of the injected fuel. The non-zoned portion of the filtercan be blank and uncatalyzed or catalyzed. This is accomplished byapplication of a coating to the full length of the filter substrate.This can be done prior to the application of oxidation catalyst zonecoating, but this is not necessary and the main body coat can be appliedafter the zone coat. The main body coat will typically (but notnecessarily) have a lower PGM loading and slurry washcoat DG than theinlet zone coat. The lower PGM affords lower cost and the lower DGaffords lower pressure-drop across the filter. It is possible to applythis coating as a separate, outlet zone coat. This can be accomplishedby applying the inlet fuel combustion zone coat to the desiredlength/depth to one end of the filter substrate and then applying theoutlet coat to the opposite end of the substrate to the desiredlength/depth. This catalyst coating is applied into the pore structureof the filter wall and does not occur as a discrete coating on thefilter wall. The composition of the main body or outlet zone coating canbe varied. Typically, the catalytic coating is comprised of PGM onalumina(s). An example catalyst has a coating comprised of 10 g/ft³Pt—Pd (10:1 ratio) supported on [SBa-150+GA-200L aluminas (50:50 wtratio) and applied to the full length of the filter support at a DG=0.25g/in³. The main body coating contributes to further combustion of anyinjected fuel that is not completely combusted on the inlet zone coat.This ensures that all the hydrocarbon and any possible partial oxidationproducts such as carbon monoxide are fully oxidized before they exit thefilter.

NOx Reducing Catalysts

For most US heavy duty diesel applications starting in 2007 enginedesign and calibration will be sufficient to meet the NOx standard. Formost US heavy duty diesel applications starting in 2007 the aftertreatment system utilizes engine design and calibration. However, in theUnited States, particularly starting in 2010, stricter NOx emissionsstandards are not expected to be met by engine design and calibrationmeasures alone and a NOx reduction after treatment catalyst will berequired. The NOx reducing catalyst according to one or more embodimentsof the invention can comprise a selective catalytic reduction (SCR)catalyst, a lean NOx catalyst, a lean NOx trap (LNT), or a combinationof these. This could also be applied to light duty diesel applications.

It should be noted that the engine-out NOx is mainly in the form of NOwith low levels of NO₂ and that the PGM loadings and ratios employed inthe zone and body of the zoned particulate filter can be tailored tocontrol the level of filter-out NO₂ versus NO. The oxidation reaction,represented by NO+½ O₂−>NO₂, can be controlled by the PGM function. Theeffectiveness of the down-stream SCR or LNT can be enhanced by controlof the NO₂/NO ratio.

For an SCR reaction, there are three reaction conditions can beconsidered depending on the NO₂/NO ratio:

(1) Standard:

4 NH₃+4 NO+O₂−>4 N₂+6H₂O

(2) “Fast”:

4 NH₃+2 NO+2 NO₂−>4 N₂+6H₂O

(3) “Slow”:

4 NH₃+3 NO₂−>3.5 N₂+6H₂O.

From the above three conditions, it can be seen that the desired “fast”or more efficient SCR reaction occurs if the NO₂ to NO ratio is 1:1 andrelative to engine-out it is expected to require an oxidation functionto increase the relative amount of NO₂. According to embodiments of theinvention, the PGM on the zoned particulate filter can contribute tothis function and tailoring the PGM loading and ratio can be used toachieve this. It is believed that the 1:1 ratio will give the bestdown-stream SCR reaction. Higher levels of NO₂ are detrimental in thatit gives a slower SCR reaction. For the LNT operation, it is necessaryto oxidize engine-out NO as fully as possible to NO₂ as LNT's absorb NOxprincipally as nitrates. Tailoring the zoned-CSF's PGM loading and ratiowould achieve this. LNT operation would be expected to require higherloading levels of PGM with most if not all the PGM in the form of Pt.

Suitable SCR catalyst compositions for use in the system are able toeffectively catalyze the reduction of the NOx component at temperaturesbelow 600° C., so that adequate NOx levels can be treated even underconditions of low load which typically are associated with lower exhausttemperatures. Preferably, the catalyst article is capable of convertingat least 50% of the NOx component to N₂, depending on the amount ofreductant added to the system. Another desirable attribute for thecomposition is that it possesses the ability to catalyze the reaction ofO₂ with any excess NH₃ to N₂ and H₂O, so that NH₃ is not emitted to theatmosphere. Useful SCR catalyst compositions used in the inventivesystem also have should resist degradation upon exposure to sulfurcomponents, which are often present in diesel exhaust gas compositions.Another suitable SCR catalyst composition comprises vanadia-titania.

Suitable SCR catalyst compositions are described, for instance, in U.S.Pat. Nos. 4,961,917 (the '917 patent) and 5,516,497, which are bothhereby incorporated by reference in their entirety. Compositionsdisclosed in the '917 patent include one or both of an iron and a copperpromoter present in a zeolite in an amount of from about 0.1 to 30percent by weight, preferably from about 1 to 5 percent by weight, ofthe total weight of promoter plus zeolite. In addition to their abilityto catalyze the reduction of NOx with NH₃ to N₂, the disclosedcompositions can also promote the oxidation of excess NH₃ with O₂,especially for those compositions having higher promoter concentrations.

Zeolites used in such compositions are resistant to sulfur poisoning,sustain a high level of activity for the SCR process. These zeoliteshave a pore size large enough to permit adequate movement of thereactant molecules NO and NH₃ in to, and the product molecules N₂ andH₂O out of, the pore system in the presence of sulfur oxide moleculesresulting from short term sulfur poisoning, and/or sulfate depositsresulting from long term sulfur poisoning. The pore system of suitablesize is interconnected in all three crystallographic dimensions. As iswell known to the those skilled in the zeolite art, the crystallinestructure of zeolites exhibits a complex pore structure having more orless regularly recurring connections, intersections and the like. Poreshaving a particular characteristic, such as a given dimension diameteror cross-sectional configuration, are said to be one dimensional ifthose pores do not intersect with other like pores. If the poresintersect only within a given plane with other like pores, the pores ofthat characteristic are said to be interconnected in two(crystallographic) dimensions. If the pores intersect with other likepores lying both in the same plane and in other planes, such like poresare said to be interconnected in three dimensions, i.e., to be “threedimensional”. It has been found that zeolites which are highly resistantto sulfate poisoning and provide good activity for both the SCR processand the oxidation of ammonia with oxygen, and which retain good activityeven when subject to high temperatures, hydrothermal conditions andsulfate poisons, are zeolites which have pores which exhibit a porediameter of at least about 7 Angstroms and are interconnected in threedimensions. While embodiments of the present invention are not to bebound by any specific theory, it is believed that the interconnection ofpores of at least 7 Angstroms diameter in three dimensions provides forgood mobility of sulfate molecules throughout the zeolite structure,thereby permitting the sulfate molecules to be released from thecatalyst to free a large number of the available adsorbent sites forreactant NOx and NH₃ molecules and reactant NH₃ and O₂ molecules. Anyzeolites meeting the foregoing criteria are suitable for use in thepractices of the present invention; specific zeolites which meet thesecriteria are USY, Beta and ZSM-20. Other zeolites may also satisfy theaforementioned criteria.

The NOx reducing catalyst may comprise a lean NOx catalyst. Lean NOxcatalysts are typically classified as either a low temperature NOxcatalyst or a high temperature NOx catalyst. The low temperature leanNOx catalyst is platinum based (Pt-based) and does not have to have azeolite present to be active, but Pt/zeolite catalysts appear to havebetter selectivity against formation of N₂O as a by-product than othercatalysts, such as Pt/alumina catalysts. Generally, a low temperaturelean NOx catalyst has catalytically active temperature ranges of about180 to 350° C. with highest efficiencies at a temperature of about 250°C. High temperature lean NOx catalysts have base metal/zeolitecompositions, for example Cu/ZSM-5. High temperature NOx catalysts havea lower temperature range of about 300-350° C. with highest efficiencyoccurring around 400° C. Different embodiments of the present inventionuse either high or low temperature lean NOx catalysts with an HCreductant.

The NOx reducing catalyst may comprise a lean NOx trap. Lean NOx trapsare disclosed in U.S. Pat. Nos. 5,875,057 and 6,471,924, the entirecontent of each patent incorporated herein by reference. In general, alean NOx trap containing a combination of a NOx sorbent and an oxidationcatalyst, which sorbs NOx onto the trap member during selected periodsof time, e.g., when the temperature of the gaseous stream is not suitedfor catalytic lean NOx abatement. During other periods of time, e.g.,when the temperature of the gaseous stream being treated is suitable forcatalytic lean NOx abatement, the combustible component on the trap isoxidized to thermally desorb the NOx from the trap member. A lean NOxtrap typically comprises a catalytic metal component such as one or moreplatinum group metals and/or a base metal catalytic metal component suchas oxides of one or more of copper, cobalt, vanadium, iron, manganese,etc.

The NOx reducing catalyst compositions can be coated onto honeycombflow-through monolith substrates formed of refractory metallic orceramic (e.g., cordierite) materials. Alternatively, oxidation catalystsmay be formed on to metallic or ceramic foam substrates which arewell-known in the art. These oxidation catalysts, by virtue of thesubstrate on which they are coated (e.g., open cell ceramic foam),and/or by virtue of their intrinsic oxidation catalytic activity providesome level of particulate removal.

According to one or more embodiments of the invention, a reductantdosing system is provided upstream of the NOx reducing catalyst anddownstream of the particulate to inject a NOx reductant into the exhauststream. As disclosed in U.S. Pat. No. 4,963,332, NOx upstream anddownstream of the catalytic converter can be sensed, and a pulsed dosingvalve can be controlled by the upstream and downstream signals. Inalternative configurations, the systems disclosed in U.S. Pat. No.5,522,218, where the pulse width of the reductant injector is controlledfrom maps of exhaust gas temperature and engine operating conditionssuch as engine rpm, transmission gear and engine speed. Reference isalso made to the discussion of reductant pulse metering systems in U.S.Pat. No. 6,415,602, the discussion of which is hereby incorporated byreference.

In the embodiment of FIG. 4, an aqueous urea reservoir 22 stores aurea/water solution aboard the vehicle which is pumped through a pump 21including a filter and pressure regulator to a urea injector 16. Ureainjector 16 is a mixing chamber which receives pressure regulated air online 19 which is pulsed by a control valve to urea injector 16. Anatomized urea/water/air solution results, which is pulsed injectedthrough a nozzle 23 into exhaust pipe 24 upstream of the NOx reducingcatalyst 11, which is upstream of the particulate filter 12, and anoptional NH₃ destruction catalyst (not shown).

This invention is not limited to the aqueous urea metering arrangementshown in FIG. 4. It is contemplated that a gaseous nitrogen basedreagent will be utilized. For example, a urea or cyanuric acid prillinjector can meter solid pellets of urea to a chamber heated by theexhaust gas to gasify the solid reductant (sublimation temperature rangeof about 300 to 400° C.). Cyanuric acid will gasify to isocyanic acid(HNCO) and urea will gasify to ammonia and HNCO. With either reductant,a hydrolysis catalyst can be provided in the chamber and a slip streamof the exhaust gas metered into the chamber (the exhaust gas containssufficient water vapor) to hydrolyze (temperatures of about 150 to 350°C.) HNCO to produce ammonia. In addition, for lean NOx catalysts,hydrocarbons generated from the engine may provide a suitable amount ofreductant for the system.

In addition to urea and cyanuric acid, other nitrogen based reducingreagents or reductants especially suitable for use in the control systemof the present invention includes ammelide, ammeline, ammonium cyanate,biuret, cyanuric acid, ammonium carbamate, melamine, tricyanourea, andmixtures of any number of these. However, the invention in a broadersense is not limited to nitrogen based reductants but can include anyreductant containing hydrocarbons such as distillate fuels includingalcohols, ethers, organo-nitro compounds and the like (e.g., methanol,ethanol, diethyl ether, etc.) and various amines and their salts(especially their carbonates), including guanidine, methyl aminecarbonate, hexamethylamine, etc.

NH₃-Destruction Catalyst Compositions

In one or more embodiments, the NH₃ destruction catalyst is composed ofa platinum group metal component dispersed on a refractory inorganicoxide support. When the NH₃ destruction catalyst is deposited on themonolith carrier, the platinum group metal component is typicallypresent at from 0.1 to 40 g/ft³, and preferably, from 0.5 to 10 g/ft³.At these concentrations the platinum group metal component is effectivefor the oxidation of ammonia to form N₂, but has a diminished propensityto cause oxidation of ammonia to form NOx. As described above, higherconcentrations of platinum in the composition are liable to promote theconversion of excess ammonia to NOx and not to N₂. Moreover, lowerlevels of platinum group metal components are desired to minimize theformation of sulfates that contribute to the mass of the particulatematter that is discharged to the atmosphere.

Suitable platinum group metal components include platinum, palladium,rhodium and iridium components. Platinum is especially suitable. Inembodiments of the invention, where platinum is used in the NH₃destruction catalyst, the platinum component can be sulfated to furthermoderate the catalytic activity of the platinum component and controlNOx formation. The sulfation can be performed by treatment of thecomposition with sulfuric acid, or alternatively, by subjecting thefinal coated composition to an exhaust stream derived from an internalcombustion engine that uses fuel that contains higher levels of sulfurcomponent (e.g., >350 ppm).A

An exemplary NH₃ destruction catalyst material is composed of platinumdispersed on one or both of bulk ceria and activated alumina. Suchcompositions are similar to those described in U.S. Pat. No. 5,462,907,the disclosure of which is hereby incorporated by reference. Thecatalytic material can be prepared in the form of an aqueous slurry ofceria and alumina particles, the particles being impregnated with the awater-dispersible or water-soluble platinum precursor. The slurry canthen applied to the carrier, dried and calcined to form a catalyticmaterial coating (“washcoat”) thereon. Typically, the ceria and aluminaparticles are mixed with water and an acidifier such as acetic acid,nitric acid or sulfuric acid, and ball milled to a desired particlesize. Alternatively the slurry can be dried and calcined before beingcoated on the carrier.

The platinum catalytic metal component is preferably incorporated intothe ceria particles or into the ceria and alumina particles. Theceria-alumina acts not only as a catalyst but also as a support for theplatinum catalytic metal component. Such incorporation with the platinumprecursor can also be conducted after the ceria-alumina catalyticmaterial is coated as a washcoat onto a suitable carrier, byimpregnating the coated carrier with a solution of a suitable platinumprecursor, followed by drying and calcination. However, preferably, theceria particles or both the ceria and alumina particles are impregnatedwith a suitable platinum precursor before a coating of the ceria-aluminacatalytic material is applied to the carrier. In either case, theplatinum metal is added to the ceria-alumina catalytic material as,e.g., a solution of a soluble platinum compound, the solution serving toimpregnate the ceria and alumina particles (or the ceria-alumina coatingon the carrier), which may then be dried and the platinum fixed thereon.Fixing can be carried out by calcination or by treatment with hydrogensulfide or by other known means, to render the metal in water-insolubleform.

Generally, the slurry of ceria and activated alumina particles, with theplatinum solution, will be deposited upon the carrier substrate anddried and calcined to adhere the catalytic material to the carrier and,to revert the platinum compound to the elemental metal or its oxide.Suitable platinum precursors for use in the foregoing process includepotassium platinum chloride, ammonium platinum thiocyanate,amine-solubilized platinum hydroxide and chloroplatinic acid, as iswell-known in the art. During calcination, or at least during theinitial phase of use of the catalyst, such compounds, if present, areconverted into the catalytically active elemental platinum metal or itsoxide.

When the catalytic material is applied as a thin coating to a suitablecarrier, such as described above, the proportions of ingredients areconventionally expressed as weight of material per gross unit volume ofcatalyst, as this measure accommodates the presence of different celldensities, wall thicknesses, gas flow passages, etc. Grams per cubicinch (“g/in³”) units are used to express the quantity of relativelyplentiful components such as the ceria-alumina catalytic material, andgrams per cubic foot (“g/ft³”) units are used to express the quantity ofthe sparsely used ingredients, such as the platinum metal. For typicaldiesel exhaust applications, the ceria-alumina catalytic materialgenerally may comprise from about 0.25 to about 4.0 g/in³, preferablyfrom about 0.25 to about 3.0 g/in³ of the coated carrier substrate, andfrom about 0.1 to 10 g/ft³ of platinum.

Optional Components

Generally, other ingredients may be added to the catalyst compositionsuch as conventional thermal stabilizers for the alumina, e.g., rareearth metal oxides such as ceria. Thermal stabilization of high surfacearea ceria and alumina to prevent phase conversion to less catalyticallyeffective low surface area forms is well-known in the art. Such thermalstabilizers may be incorporated into the bulk ceria or into the bulkactivated alumina, by impregnating the ceria (or alumina) particleswith, e.g., a solution of a soluble compound of the stabilizer metal,for example, an aluminum nitrate solution in the case of stabilizingbulk ceria. Such impregnation is then followed by drying and calciningthe impregnated ceria particles to convert the aluminum nitrateimpregnated therein into alumina.

In addition, the catalyst compositions may contain other catalyticingredients such as other base metal promoters or the like. However, inone embodiment, the catalyst composition of the present inventionconsists essentially only of the high surface area ceria and highsurface area alumina, preferably present in a weight proportion of 1.5:1to 1:1.5, with or without thermal stabilizers impregnated therein, and,from 0.1 to 10 g/ft³ of platinum.

EXAMPLES

The following examples further illustrate the present invention, but ofcourse, should not be construed as in any way limiting its scope.

Example 1 Preparation of Zone Coated Catalyzed Particulate Filter Sample

A zoned catalyzed soot filter (CSF) consistent with this invention wasprepared as follows:

A cordierite wall-flow filter substrate (Corning CO) having a roundcross section with dimensions of 10.5″ dia.×12.0″ long and having a cellspacing of 200 cpsi with a filter wall thickness of 0.012″ was used. Thecoating of this substrate consisted of:

a. An optional first coating of fugitive water soluble polymer, RhoplexP-376 (Rohm & Haas) applied to the entire substrate that after dryingresulted in a DG=0.25 g/in³. One purpose of this polymer coating is tofill the smallest of pores in the cordierite filter porosity, therebyallowing better distribution of the subsequent catalytic coating in thewall of the filter substrate.

b. A first catalytic coating applied to the full length of the wall flowfilter substrate. This coating was comprised of platinum and palladiumimpregnated onto a 50:50 wt mixture of lanthanum stabilized alumina,GA-200L (Engelhard), containing 4% La₂O₃ and alumina, SBa-150 (SasolNorth America). Platinum was first impregnated onto the mixture ofaluminas as an aqueous solution of monoethanol-amine stabilized Pt (IV)hydroxide and then with palladium as an aqueous solution of Pd (II)nitrate. The resulting PGM impregnated alumina mixture with Pt to Pdratio of 10:1 was milled in water to achieve a particle sizedistribution with 90% less than 7 microns, following which the resultantslurry was adjusted for pH=4 and solids for coating. The first catalyticcoating was applied to the full length of the wall flow filter substratein one pass to achieve a DG=0.26 g/in³ and having a total Pt+Pd loadingof 10 g/ft³ with a Pt to Pd ratio of 10:1.

c. A second, zone catalytic coat was then applied to the inlet end ofthe wall flow filter substrate to a length (depth) of 3″. This coatingwas comprised of platinum and palladium impregnated onto a 50:50 wt.mixture of lanthanum stabilized alumina, GA-200L (Engelhard), containing4% La₂O₃ and alumina, SBa-150 (Sasol North America). Platinum was firstimpregnated onto the mixture of aluminas as an aqueous solution ofmonoethanol-amine stabilized Pt (IV) hydroxide and then with palladiumas an aqueous solution of Pd (II) nitrate. The resulting PGM impregnatedalumina mixture with Pt to Pd ratio of 10:1 was milled in water toachieve a particle size distribution with 90% less than 7 microns,following which the resultant slurry was adjusted for pH=4 and solidsfor coating. The second, zone catalytic coating was applied to the inlet3″ of the wall flow filter substrate in one pass to achieve a DG=0.53g/in³ within the zone and having a total Pt+Pd loading of 60 g/ft³ witha Pt to Pd ratio of 10:1.

This resulted in a zoned catalyzed soot filter (CSF) having an overalltotal Pt+Pd loading level of 25.0 g/ft³ with overall Pt to Pd ratio of10:1.

Example 2 Fuel Light-Off Over Zoned CSF

In order to demonstrate active regeneration capability of the zoned CSFa fuel light-off test in the engine test cell was conducted. Thistesting was run using a turbocharged 7.6 liter, 225 HP diesel engineinstalled in an engine test cell and connected to a dynamometer. Thetesting was conducted using the zoned catalyzed soot filter (CSF)described in Example 1, above.

For the light-off testing the zoned catalyzed soot filter (CSF) wasmounted in the exhaust line of the engine in a position 10 ft.downstream of the engine's turbocharger. The exhaust line was equippedwith a fuel injector through which supplemental diesel fuel could beintroduced into the exhaust stream. This fuel injector was a standardtype used for gasoline engines and it was mounted just downstream of theengine's turbocharger. Between the diesel fuel injector and the zonedcatalyzed soot filter (CSF) was mounted an inline mixer to assist mixingof the atomized, injected fuel with the exhaust stream. All tests wereconducted using ultra low sulfur (<15 ppm S) diesel fuel both for engineoperation and supplemental fuel injected into the exhaust.

For the test the engine was operated at a speed of 1570 rpm and a torqueof 745 Nm which resulted in a total exhaust flow of 740 std. m³/hr withan exhaust temperature at the inlet of the zoned catalyzed soot filter(CSF) of 300° C. as measured by a thermocouple mounted just upstream ofthe face of the CSF. A thermocouple was also mounted just downstream ofthe CSF outlet face to measure the exhaust temperature at that location.

Starting with a relatively clean, soot free zoned catalyzed soot filter(CSF) the system was allowed to equilibrate and stabilize fortemperature. Following this (ca. 122 minutes runtime), diesel fuel wasintroduced at varying levels into the exhaust via the fuel injectordescribed above and the exhaust temperatures at the inlet and outlet ofthe CSF were monitored. The results are shown in FIG. 5. Initially theCSF in and CSF out exhaust temperatures were the same (300° C.), but asincreasing amounts of fuel were injected into the upstream exhaust theCSF outlet temperature increased. For one segment (ca. 130-135 minutesruntime) with 1.2 g/sec diesel fuel injected into the exhaust the CSFoutlet exhaust gas temperature was 545° C. which was an increase of 245°C. above the inlet exhaust gas temperature. This exhaust temperature isin the range sufficient to give soot combustion in the filter underactive regeneration conditions. Measurement of the exhaust gas totalhydrocarbon content during this segment showed ca. 13,000 ppm C1 at theCSF inlet location, but only 2.7 ppm C1 at the CSF outlet indicatingessentially complete combustion of the supplemental injected diesel fuelin the CSF.

FIG. 6 shows the inlet vs. outlet exhaust temperature data for thelight-off test above as a function of the rate of injection of dieselfuel into the exhaust up stream of the zoned catalyzed soot filter(CSF). This shows a regular increase in CSF out exhaust temperature withincrease in injected diesel fuel and that temperatures of 600° C. can beattained for injection rates of 1.5 g/sec. At some injection rate levelsthe exhaust temperature data appears as bar or range which reflects thetemperature-time heat up response on changing from one injection rate tothe next higher one.

Example 3 Fuel Light-Off Testing with Temperature Measurements in theZoned Catalyzed Soot Filter (CSF) Bed

The test in EXAMPLE 2 above measured the effect of light-off of injectedfuel on exhaust gas temperatures under one engine speed and loadcondition. CSF out exhaust temperatures as high as 600° C. were attainedwhich are in a good range for achieving reasonably rapid combustion ofsoot in the CSF for active regeneration.

The test of EXAMPLE 3 extended investigation to include measurement oftemperatures within the zoned catalyzed filter. These measurementsallowed characterization of both axial and radial distribution oftemperatures within the CSF to demonstrate how the light-off of injectedfuel developed and its uniformity. Further, the temperatures within theCSF were more representative of local temperatures in the same regionswhere the soot combustion was taking place during active regeneration.

In addition the tests of EXAMPLE 3 were conducted at different enginespeeds that gave different exhaust flows, plus different torque levelswere employed at these speeds to give lower CSF inlet exhausttemperatures than were run for EXAMPLE 2.

For these tests the same engine and test set up were used as in EXAMPLE2, except that the zoned catalyzed soot filter (CSF) was fitted withinternal thermocouples to measure the internal filter temperatures. Ten(10) thermocouples were installed in the filter in a configuration shownin FIG. 7. This configuration consisted of five (5) thermocouplesinstalled down the centerline of the filter to measure the temperaturesin the very middle of the filter body. These thermocouples werepositioned at 1″ from the inlet face (TC1), 3″ from the inlet face andat the rear of the inlet zone (TC2), 6″ from the inlet face and at thefilter axial mid-point (TC3), 9″ from the inlet face (TC4) and 11″ fromthe inlet face (TC5). In addition five (5) thermocouples were installedin a line that was located 1″ radially from the outer edge of the zonedcatalyzed soot filter and were at corresponding positions from the inletface of the filter of 1″ (TC11), 3″ (TC12), 6″ (TC13), 9″ (TC14) and 11″(TC15).

The thermocouples used in EXAMPLE 2 to measure exhaust gas temperaturesnear the inlet and outlet faces of the CSF were also in place forexhaust gas temperature measurement in this test.

The testing consisted of running light-off tests with injected fuel atthree characteristic engine speeds: A-speed=1580 rpm, B-speed=1940 rpmand C-speed=2680 rpm. The injected fuel rate was held constant at eachspeed condition and the engine torque was varied to give different inletexhaust gas temperatures between 350° C. and 250° C. Stabilizedtemperatures were recorded for inlet and outlet exhaust gas and for theinternal thermocouples installed in the CSF.

The results for the A-speed tests are given in TABLE I, below:

TABLE I A-Speed Data for Fuel Light-Off A-Speed = 1580 rpm FuelInjection Rate = 1.66 g/sec Test Point 1 2 3 4 Exhaust Flow (std. m3/hr)739 720 700 682 Zoned CSF-In Gas Temp. (C.) 305 285 268 256 ZonedCSF-Out Gas Temp. (C.) 658 629 604 607 Filter Internal Temperatures: TC1Centerline 1″ in Temp. (C.) 498 454 433 419 TC2 Centerline 3″ in Temp.(C.) 537 499 470 465 TC3 Centerline 6″ in Temp. (C.) 599 565 533 532 TC4Centerline 9″ in Temp. (C.) 663 634 604 608 TC5 Centerline 11″ in Temp.(C.) 700 669 635 641 TC11 Edge 1″ in Temp. (C.) 489 446 408 351 TC12Edge 3″ in Temp. (C.) 528 488 465 455 TC13 Edge 6″ in Temp. (C.) 598 565533 531 TC14 Edge 9″ in Temp. (C.) 653 615 589 592 TC15 Edge 11″ inTemp. (C.) 700 669 635 641

With a diesel fuel injection rate of 1.66 g/sec and for inlet exhausttemperatures in the range of 305° C. to 256° C. and exhaust flows in therange of 739-682 std. m³/hr it was possible to achieve CSF outletexhaust temperatures in the range of 658° C. to 607° C. which give agood range for reasonably rapid soot combustion in a filter.

Furthermore, high internal temperatures >500° C. within the filter couldbe attained over much of the length of the filter which are sufficientto give reasonably rapid soot combustion from the filter. The internaltemperatures down the centerline of the filter and 1″ from the outeredge of the filter showed good radial uniformity of temperature in thefilter during the light-off test. The internal temperatures measured atthe position 1″ in from the inlet face of the filter were lower thanthose measured further in from the inlet face, but this isunderstandable in that light-off of the injected fuel was beinginitiated in this region. Still the internal temperatures 1″ in from theinlet face of the CSF were 163° C. to 193° C. higher than the inletexhaust gas temperature.

The exhaust gas and internal substrate temperatures for A-speed testpoint 1 (305° C. inlet gas temperature) are shown graphically in FIG. 8.It can be seen that there was essentially a linear increase in internalsubstrate temperature down the length of the CSF with temperatures >500°C. over most of the length of the CSF to facilitate reasonably rapidsoot combustion in the filter for active regeneration. Furthermore, theCSF internal temperatures at the centerline of the filter and 1″ fromthe outer edge of the filter were nearly identical which showed gooduniformity of light-off and active fuel burning.

The results for the B-speed tests are given in TABLE II, Below:

TABLE II B-Speed Data for Fuel Light-Off B-Speed = 1940 rpm FuelInjection Rate = 2.25 g/sec Test Point 1 2 3 4 Exhaust Flow (std. m3/hr)979 968 935 928 Zoned CSF-In Gas Temp. (C.) 294 281 271 261 ZonedCSF-Out Gas Temp. (C.) 646 652 657 656 Filter Internal Temperatures: TC1Centerline 1″ in Temp. (C.) 463 458 447 431 TC2 Centerline 3″ in Temp.(C.) 498 497 489 482 TC3 Centerline 6″ in Temp. (C.) 551 560 556 556 TC4Centerline 9″ in Temp. (C.) 631 645 645 638 TC5 Centerline 11″ in Temp.(C.) 679 696 698 698 TC11 Edge 1″ in Temp. (C.) 447 423 375 326 TC12Edge 3″ in Temp. (C.) 491 490 480 467 TC13 Edge 6″ in Temp. (C.) 550 557549 543 TC14 Edge 9″ in Temp. (C.) 610 621 621 616 TC15 Edge 11″ inTemp. (C.) 673 691 691 691

These results were similar but for a higher exhaust volumetric flowcondition and thus shorter contact time than for the A-speed tests. CSFoutlet exhaust gas temperatures and internal filter temperatures in therange of 500° C. to ca. 700° C. should were attained which would givereasonably rapid combustion of soot from the filter under these activeregeneration conditions.

The results from the C-speed tests are given in TABLE III,

below:

TABLE III C-Speed Data for Fuel Light-Off C-Speed = 2680 rpm FuelInjection Rate = 1.80 g/sec Test Point 1 2 3 4 5 6 7 Exhaust Flow (std.m3/hr) 969 917 874 830 770 723 713 Zoned CSF-In Gas Temp. (C.) 351 330317 301 281 262 251 Zoned CSF-Out Gas Temp. (C.) 645 650 651 651 659 668678 Filter Internal Temperatures: TC1 Centerline 1″ in Temp. (C.) 515503 499 492 479 460 448 TC2 Centerline 3″ in Temp. (C.) 546 535 531 527524 505 511 TC3 Centerline 6″ in Temp. (C.) 590 584 582 581 585 586 587TC4 Centerline 9″ in Temp. (C.) 649 650 651 653 665 670 685 TC5Centerline 11″ in Temp. (C.) 679 685 686 689 702 712 730 TC11 Edge 1″ inTemp. (C.) 513 503 498 491 478 457 446 TC12 Edge 3″ in Temp. (C.) 540532 527 525 519 504 503 TC13 Edge 6″ in Temp. (C.) 587 582 579 578 584586 587 TC14 Edge 9″ in Temp. (C.) 634 633 633 634 648 653 665 TC15 Edge11″ in Temp. (C.) 673 678 682 682 697 712 730

The results for these tests were similar and showed good light-off ofinjected fuel that gave high enough CSF outlet gas temperatures andinternal filter temperatures to give reasonably rapid soot combustionfrom the filter under active regeneration.

Example 4 Active Regeneration of Zoned Catalyzed Soot Filter with SootLoading in the Filter

The same zoned catalyzed soot filter (CSF) used for testing in EXAMPLES1-3 was loaded with soot on a 6.6 liter 330 HP engine at a speed of 3200rpm and torque of 125 Nm. The soot loaded filter (2.8 g/liter soot) wasplaced in the exhaust line of the 7.6 liter 225 HP engine employed inEXAMPLES 2-3 and which was equipped with the same supplemental dieselfuel injector used for active regeneration. The engine was adjusted to aspeed of 1566 rpm and torque of 680 Nm to achieve a CSF inlet exhaustgas temperature of 303° C. with exhaust flow of 705 std. m³/hr. Oncestabilized the pressure drop (Delta P) across the filter under theseconditions was measured as 8.57 KPa. Supplemental diesel fuel injectioninto the exhaust (1.62 g/sec) was established to initiate an activeregeneration which was continued for ca. 25 min. The results of thisactive regeneration are shown in FIG. 9. It can be seen that the CSF outexhaust gas temperature increased with supplemental fuel injection to alevel of 656° C. suitable for active soot combustion. The level of DeltaP also increased with increase in exhaust temperature but reached a peakof ca. 11.5 KPa after ca. 2 min. of runtime, following which Delta P wasreduced and at the end of the run was ca. 9.3 KPa with outlet exhausttemperature at 656° C. for a reduction of 2.2 KPa from peak Delta P. Thesupplemental fuel injection was then terminated and the CSF out exhaustgas temperature returned to the same level as the CSF in exhaust gastemperature (303° C.). The level of Delta P across the filter at thispoint was measured as 5.87 KPa for a reduction of 2.70 KPa relative tothe level before the active regeneration. Weighing of the filter afterthe active regeneration showed a 60% reduction in the level of soot inthe filter. This was not considered to be an optimized process or test,but it clearly demonstrated active regeneration with the zoned catalyzedfilter (CSF) for reduction of filter Delta P and soot loading.

Example 5

A system consisting of a urea/fuel injector, a BASF REX-1848 V/Ti SCRcatalyst, and a zoned CSF with a length of 15 inches and a diameter of12 inches prepared according to the method described in Example 1 wasput in the exhaust stream of a turbocharged diesel engine. A schematicdrawing of the system is shown in FIG. 10. The engine was operated atseveral steady state conditions. The table shows the NO_(x) conversionover the SCR catalyst at various conditions.

SCR inlet T (° C.) GHSV (h⁻¹) NH₃/NO_(x) NO_(x) conversion (%) 369 1181.0 81 368 58 1.0 90 305 92 1.0 81 306 46 1.0 93

Example 6

The system described in Example 5 was actively regenerated by injectingdiesel fuel through the injector upstream of the SCR catalysts. Theamount of fuel was controlled to sequentially reach 550° C., 600° C.,and 650° C. for 20, 10 and 10 min respectively.

Example 7

The SCR activity of the system described in Example 5 was measured afterthe active regeneration of Example 6. Results are shown in the table andare identical within the accuracy of the test to the results obtained inExample 5. The data shows that the injection of diesel fuel did notnegatively impact the performance of the SCR catalyst.

SCR inlet T (° C.) GHSV (h⁻¹) NH₃/NO_(x) NO_(x) conversion (%) 367 1161.0 81 367 59 1.0 91 306 91 1.0 81 306 46 1.0 94

Example 8

A zeolitic SCR catalyst was prepared by ion-exchanging zeolite g to a Cucontent of 2 wt % and coating the resulting catalyst on a substrate at aloading of 2.9 g in⁻³. An NH₃ oxidation (AMOX) catalyst was prepared byimpregnation a Fe/β catalyst sequentially with Pt (0.17 wt %) and Cu(9.6 wt % as CuO). The SCR and the AMOX catalyst and a zoned CSF with alength of 15 inch and a diameter of 12 inch prepared according to themethod described in Example 1 was put in the exhaust stream of aturbocharged diesel engine with the CSF downstream of the SCR catalyst.The engine was operated at several steady state conditions. The tableshows the NOx conversion over the SCR catalyst at various conditions.

SCR inlet T (° C.) GHSV (h⁻¹) NH₃/NO_(x) NO_(x) conversion (%) 368 88.10.97 86.1 367 43.8 0.96 90.2 305 71.6 1.06 87.8 303 35.4 1.07 100

Example 9

The system described in Example 7 was actively regenerated by injectingdiesel fuel through the injector upstream of the SCR catalysts. Theamount of fuel was controlled to sequentially reach 550° C., 600° C.,and 650° C. for 20, 10 and 10 min respectively.

Example 10

The SCR activity of the system described in Example 7 was measured afterthe active regeneration of Example 8. Results are shown in the table andare identical within the accuracy of the test to the results obtained inExample 7.

SCR inlet T (° C.) GHSV (h⁻¹) NH₃/NO_(x) NO_(x) conversion (%) 376 88.70.99 85.5 376 44.4 0.99 91.4 308 71.8 1.10 89.3 307 35.7 1.10 100

While the foregoing is directed to embodiments of the present invention,other and further embodiments of the invention may be devised withoutdeparting from the basic scope thereof, and the scope thereof isdetermined by the claims that follow.

1. An emission treatment system for treatment of an exhaust stream comprising NO_(x) and particulate matter, the emission treatment system comprising: a particulate filter having an axial length and elements for trapping particulate matter contained in an exhaust stream flowing through the filter and a light-off oxidation catalyst composition extending from the inlet end towards the outlet end to a length that is less than the axial length of the walls to provide an inlet zone in an amount sufficient to light-off at a temperature less than about 300° C. and generate an exotherm to burn soot trapped in the filter; and a NOx reducing catalyst located upstream of the wall flow monolith.
 2. The emission treatment system of claim 1, wherein the particulate filter comprises a wall flow monolith disposed within the exhaust stream and having a plurality of longitudinally extending passages bounded by longitudinally extending walls, the passages comprising inlet passages having an open inlet end and a closed outlet end, and outlet passages having a closed inlet end and an open outlet end, the walls having a porosity of at least 40% with an average pore size of at least 5 microns and the wall flow monolith comprising a light-off oxidation catalyst composition permeating the walls.
 3. The emission treatment system of claim 1, further comprising an NH₃ destruction catalyst located downstream from the NO_(x) reducing catalyst.
 4. The emission treatment system of claim 1, wherein the NO_(x) reducing catalyst comprises a lean NO_(x) catalyst.
 5. The emission treatment system of claim 4, further comprising a reductant introduction port in fluid communication with a hydrocarbon reductant, the reductant introduction port located upstream from the lean NOx catalyst.
 6. The emission treatment system of claim 4, wherein the NO_(x) reducing catalyst comprises a lean NOx trap.
 7. The emission treatment system of claim 4, wherein the NO_(x) reducing catalyst comprises an SCR catalyst.
 8. The emission treatment system of claim 6, further comprising an introduction port located upstream from the SCR catalyst, the introduction port in fluid communication with an ammonia or ammonia precursor.
 9. The emission treatment system of claim 6, further comprising an injector in fluid communication with the introduction port, the injector configured to periodically meter the ammonia or an ammonia precursor into the exhaust stream.
 10. The emission treatment system of claim 7, further comprising an NH₃ destruction catalyst located downstream from the SCR catalyst.
 11. The emission treatment system of claim 1, further comprising an exotherm-producing agent introduction port located upstream of the wall flow monolith, the exotherm-producing agent introduction port in fluid communication with an exotherm-producing agent capable of generating a temperature sufficient to periodically burn particulate accumulated in the wall-flow monolith.
 12. The emission treatment system of claim 11, wherein the exotherm-producing agent comprises diesel fuel.
 13. An emission treatment system for treatment of an exhaust stream comprising NO_(x) and particulate matter, the emission treatment system comprising: a wall flow monolith disposed within the exhaust stream and having a plurality of longitudinally extending passages bounded by longitudinally extending walls, the passages comprising inlet passages having an open inlet end and a closed outlet end, and outlet passages having a closed inlet end and an open outlet end, the walls having a porosity of at least 40% with an average pore size of at least 5 microns and the wall flow monolith comprising a light-off oxidation catalyst composition permeating the walls and extending from the inlet end towards the outlet end to a length that is less than the axial length of the walls to provide an inlet zone; an SCR catalyst located upstream of the wall flow monolith; and an injector for injecting ammonia or ammonia precursor into the exhaust gas stream upstream of the SCR catalyst.
 14. The emission treatment system of claim 13, wherein the SCR catalyst comprises zeolite.
 15. The emission treatment system of claim 13, wherein the SCR catalyst comprises vanadia.
 16. The emission treatment system of claim 13, further comprising an NH₃ destruction catalyst located downstream from the SCR catalyst.
 17. The emission treatment system of claim 16, comprising an exotherm-producing agent injector located upstream of the wall-flow monolith.
 18. A method of treating exhaust stream from a diesel engine comprising: disposing within the exhaust stream containing particulate matter a wall flow monolith and having a plurality of longitudinally extending passages bounded by longitudinally extending walls, the passages comprising inlet passages having an open inlet end and a closed outlet end, and outlet passages having a closed inlet end and an open outlet end, the walls having a porosity of at least 40% with an average pore size of at least 5 microns and the wall flow monolith comprising a light-off oxidation catalyst composition permeating the walls and extending from the inlet end towards the outlet end to a length that is less than the axial length of the walls to provide an inlet zone; disposing a NOx reducing catalyst upstream the wall flow monolith; and periodically introducing an exotherm-producing agent upstream of the wall flow monolith to generate an exotherm in the wall flow monolith sufficient to combust particulate matter trapped within the wall flow monolith. 